Sodium Carbonate → 4,4'-Difluoro-2-nitro-1,1'-biphenyl

HRID 1776195

反応式

HRID 1776195 の反応式
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[F:12][C:13]1[CH:18]=[CH:17][C:16](B(O)O)=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C(OCC)C>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:16]2[CH:17]=[CH:18][C:13]([F:12])=[CH:14][CH:15]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

参加物

9

反応物 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 676591-Chloro-4-fluoro-2-nitrobenzeneHCID 2856454-Fluorophenylboronic acid

生成物 1

HCID 3454114,4'-Difluoro-2-nitro-1,1'-biphenyl収率 52%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
165 °C

実験手順

A microwave reaction vessel was charged with 2-chloro-5-fluoronitrobenzene (0.878 g, 5.0 mmol), 4-fluorophenylboronic acid (0.770 g, 5.5 mmol), sodium carbonate (1.590 g, 15.0 mmol), palladium diacetate (0.045 g, 0.2 mmol), tetrabutylammonium bromide (1.612 g, 5.0 mmol) in water (10 mL). The mixture was heated to 165° C. in a microwave reactor for 10 mins. The reaction was cooled to room temperature and poured into diethyl ether and 0.1N aqueous sodium hydroxide. The organic layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes) to give the desired product as a yellow solid (0.61 g, 52%). 1H NMR (CDCl3, 300 MHz) δ 7.61 (dd, 1H, J=8.1, 2.7 Hz), 7.44-7.30 (m, 2H), 7.30-7.21 (m, 2H), 7.16-7.07 (m, 2H).

後処理

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled to room temperature
  3. washThe organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes)

出典と根拠

ORDレコード
ord-fbf307eac0ea4eb5975156187f04bf2a
出典データセット
uspto-grants-2016_02
特許番号
US09265772B2

関連ノート

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